Manganese peroxid sulfate and process of making same.



UNITED I STATES PATENT OFFICE.

MA'x BAZLEN, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, \ASSIGNOR rO BADISCHE ANILIN UND SODA FABRIK, OF LUDWIGSHAFEN-ON-THE- BHINE, GERMANY, A CORPORATION.

' [I MANGANESE PEROXID SULFAT E AND PROCESS OF MAKING SAME.

No. se7,777.

Specification of Letters Patent.

Patented Dec. 4, 1906.

Application filed September 2,1903- Serial No. 171.701.

To all whom-it may concern:

Be it known that 1, Max BAZLEN, a subject of the King of lVi'lrtemberg, residing at Ludwigshafen-on-tlie-Rhine, in the Kingdom of Bavaria, Empire of Germany, have invented new and useful Improvements in Manganese Peroxid Sulfate, and Processes of Making the Same, of which the following is a specification.

I have discovered a process for manufacturing a'sulfate of a higher oxid of manganese, to which substance I will refer as manganese peroxid sulfate. I prepare this substance by the oxidation in the presence of sulfuric acid of a manganese body,such as metallic manganese, an alloy of manganese, or a manganous or manganic sulfate or by the reduction, also in the presence of sulfuric acid, of permanganates. The oxidation can be performed either electrolytically or" by means of chemical oxidizing agents. The reduction can conveniently be effected by chemical agents.

My new manganese peroxid sulfate, which has a.const-itution corresponding to the formula Mn(SO is in the solid form a black substance. It is only stable in the presence of sulfuric acid containin about forty-eight percent. or more of n sa, in which it dissolves,yielding a dee -brown to black solution. In substantial y more dilute sulfuric acid or water it decomposes more or less rapidly, the decomposition being the more rapid the weaker the sulfuric acid is. These solutions in sulfuric acid containing forty-eight per cent. or more of H SO can be heated to a temperature of from about to 80 centigrade without appreciable decomposition taking place, but on continued boiling oxygen escapes and manganio sulfate is formed. On pouring a sulfuric-acid solution into water a brown solution is at first obtained; but this suddenly becomes discolored and hydrated manganese peroxid is precipitated.

The electrolytic oxidation of the manganese body to manganeseperoxid sulfate can be performed in the presence of not too dilute sulfuric acidfor instance, such as contains from forty-eight to seventy-eight per cent. of H 80, at a moderately-high temperature say from about 50 to 60 centigradeand with a current of-high density; but in some cases it is preferable to work at a somewhat lower temperature-say at from 20 to 30 centigrade. Not all substances that are employed as anodes in such electrolytic operations are suitable for -the purposes of my invention, but among those which are adapted are lead, manganese, or manganese alloys. Oxidiz'ing agents which are suitable for the purposes of my invention are permanganates,

lead peroxid, chromates, and chlorates, while as reducing agents I can'employ, among others, sulfurous acid, ferrous salts, or manganous salts.

The amount of manganese peroxid sulfate contained in a solution or solid can be arrived at by analysis. The manganese is determined in the usual manner after having reduced it to a manganous salt. The uantity of active oxygen can be determined by the aid of ferrous ammonium sulfate. The free sulfuric acid can be determined by red, cing the salt with somewhat more than the necessary quantity of sodium sulfite and then titrating with normal caustic-soda solution, The total sulfuric acid can be determined by titrating with normalcausticsoda solution, the latter being added at first in insufficient quantity to completely neutralize the whole, whereupon the solution is heated, filtered from manganese peroxid,which separates out,

the precipitate washed, and the titration of the filtrate then completed. The results of such an analysis-show that the manganese peroxid sulfate possesses a constitution corresponding to the formula-Mn (S0,),

The following examples will serve to further illustrate the nature of my invention, but it is not confined to these examples. The parts are by weight.

Example 1. Man anese Pcroacid Snl ate from Manganese Sug ate by Means of Dissolve four hundred (400) parts of finely powdered manganous sulfate (MnSO AH O) in four thousand three hundred and thirty (4,330) parts of hot sulfuric'acid containing about fifty-five and a half.. (55%) per cent. of H Pour the solution into a vessel provided with a suitable diaphragm and stir well and oxidize by means of a lead anode at a temperature of from fifty to sixty. degrees centigrade (5060 C.) The cathode con sists of lead in sulfuric acid containing about lectrolyfifty-five and a half (55%) per cent. of H SO The current density at the anode should be from about fifteen to sixteen (:16) am .peres per square decimeter. Continue the 2. Manganese Peroee'al Salfatefrom Example Manganese by Electrolysis.

Introduce into the anode department of an electrolytic cell sulfuric acid containing about seventy-eight (78) per cent. of H 80, and employ pure manganese or ferromanganese containin about ei hty (80) per cent. of Mn as anode? The cat ode consists of lead and 'is also surrounded with sulfuric acid containing about-seventy-ei ht (78) per cent. of H 80 Electrolyze wit a current of high density and about four (4) volts electrometive force at a temperature of from twenty to thirty degrees centigrade (ZO -C.) Add from-time to time suflicient manganous sulfate.- Evolution of oxygen .ishardly to be observed and a deep-brown solution ofv manganese peroxid sulfate is obtained. In em- R e ric sul ate 18 also formed, WhlC 1n concen trated solutions is usually mixed with manganese peroxid sulfate.

When electrolyzing sulfuric acid by means of manganese or ferromanganese, as above explained, a certain-amount of permanganic acid anhydrid-may be formed, which is reduced by the addition of corresponding quantities of manganous sulfate. It is also advantageous to employ more concentrated sulfuric acid than in Example 1, as sulfuric acid is used up in forming the sulfate of man ganese peroxid.

Example 3. Manganese Perom'd Salfatefrom a Manganese Salt by Means of an Oxidizt'ng Agent. Into a solution of manganous sulfate in sulfuric acid containing from about forty-eight to seventy-eight (48-78) per cent. of H SO and at a temperature of from fifty to sixty degrees oentigrade (50"60 C.) add, while stirring, lead peroxid free from chlorin. A red solution or a precipitate of manganic sul fate is at first obtained, which on further ad dition of lead peroxid is converted, with the separation of lead sulfate, into a brown solution of manganese peroxid sulfate.

ferromanganese a preci itate of ferof this salt separates out.

Instead of lead. peroxid other oxidizing agents can be employed.

Example 4. Manganese Peroaid Sulfate by the Interaction of Mangano as Sulfate and Permanganate.

a. In s0lati0n.Dissolve one hundred and sixty-nine (169) parts of manganous sulfate dried at one hunderd and fifty degrees centigrade (150 C.) (MnSO .H O) in forty-seven hundred and eighty (4,780) parts of sulfuric acid containing about seventy (70) per cent. of H 50, and add one hundred and eight (108) parts of finely-powdered potassium permanganate in smallportions atatemperature of from fifty to sixty degrees centigrade (SW- 0.)while stirring well. Red manganic sulfate is at first formed. It is then convertedinto' the brown manganese peroxid sulfate. Instead of manganous sulfate the equivalent quantity of manganic sulfate can be employed, in which caseonly half the above quantity of permanganate is necessary. v w

- b. In the s0liclf0'rm.-To twenty-nine hundred (2,900) parts of sulfuric acid containing about fifty-five and a'half (55%) per cent. of H SO add six hundred and sixty-nine (669) parts of finely-divided manga'nous sulfate (MnSO,.4H O) at a temperature of from fifty to sixty degrees centigrade (5060 C.) and then three hundred and sixteen (316) parts of potassium permanganate at first quickly, then slowly. A deep black solution of manganese peroxid sulfate is obtained, from which, to begin with, but little ever, manganese peroxid sulfate separates out in solid form.

' I claim 1. The process of manufacturing inanganese peroxid sulfate by subjecting a hereinhefore-defined manganese body to oxidation in the presence of sulfuric acid containing'at least about forty-eight per cent. H SO substantially as described.-

2. As a new article of manufacture, man- 'ganese peroxid sulfate, which in the. solid orm is black, which possesses a constitution.

corresponding to the formula Mn ($0 which dissolves in cold sulfuric acid containing from forty-eight to seventy-eight per cent. H SO yielding from brown to black so- On cooling, howlutions which solutions yield on boiling oxygen and manganic sulfate.

In testimony whereof I have hereunto set my hand in the presence of two subscribing Witnesses.

a v MAX BAZLEN.

Witnesses:

ERNEST F. EHRHARDT, JAcoB ADRIAN. 

